Complexes of 2-heptadecylimidazolines



United States Patent tive of such chelates are: di(heptadecylimidazoline acetic acid) magnesium sulfate, di(heptadecylimidazoline acetic acid) magnesium chloride, di(heptadecylimidazoline acetic acid) zinc chloride, di(heptadecylimidazoline acetic COMPLEXES F Z-HEPTADECYLIMIDAZOLINES 5 acid) cadmium sulfate, di(heptadecylimidazoline acetic acid) cadmium nitrate di(heptadecylimidazoline acetic h 1 k gg a gggg gag zg i ig gfii ac d) mercury sulfate and d1(heptadecyl1m1dazolme acetic acid) mercurybromide. No Drawing. Application March 11,1957 The compositions of my invention also include the Serial No. 645,016 chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group III of the periodic table. 10 C] I m (CL 260-299) Illustrative of such chelates are: triheptadecylimidazoline aluminum sulfate, triheptadecylimidazoline aluminum nitrate and triheptadecylimidazoline aluminum chloride. This invention relates to complexes of 2-heptadecyl- My compositions also include chelates formed by reimidazolines and to a process for their preparation. acting acid salts of 2-heptadecylimidazoline with the salts More particularly, this invention relates to chelates of of the metals of group III of the periodic table. Illus- Z-heptadecylimidazolines, as new compositions of mattrative of such chelates are: tri(heptadecylimidazoline ter and to a process for their preparation. acetic acid) aluminum sulfate, tri(heptadecylimidazoline I have discovered that novel chelates of Z-heptadecylacetic acid) aluminum nitrate and tri(heptadecylimidazoimidazolines are formed by reacting a metallic compound line acetic acid) aluminum chloride. with a2-heptadecylimidazoline. The compositions of my invention also include the An embodiment of the present invention is a class chelates formed by reacting 2-heptadecylimidazoline with of new compositions of matter which are chelates formed the salts of the metals of group IV of the periodic table. by reacting a metallic salt with a Z-heptadecylimidazo- Illustrative of such chelates is diheptadecylimidazoline line. A specific chelate, which is illustrative of this emlead nitrate. bodiment of my invention is tri(Z-heptadecylimidazoline Still other compositions within the scope of my invenacetic acid) chromium III sulfate (C H O N S Cr tion are the chelates formed by reacting the acid salts of which can be represented by the structural formula 2-heptadecylimidazo1ine with the salts of the metals of HOOCCH:

H I Q 11000011 IFOOCCHQ C C-Gi7Ha5 3 5 (IE I N r: /N\ 4): CirHs5C \CH2 (3H2 C-C11 e5 nt -(3H, GHQ-h Or J2 Tri(Z-heptadecylimidazoline acetic acid) chromium III sulfate,

These compositions include the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group I of the periodic table. Illustrative of such chelates are: diheptadecylimidazoline silver nitrate and diheptadecylimidazoline copper sulfate.

My compositions also include chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group I of the periodic table. II- lustrative of such chelates are: di(heptadecylimidazoline acetic acid) sodium sulfate, di(heptadecylimidazoline acetic acid) sodium hypophosphate, di(heptadecylimidazoline acetic acid) silver nitrate, di(heptadecyli1nidazoline acetic acid) copper sulfate.

The chelates of my invention can also be formed by reacting Z-heptadecylimidazoline with the salts of the metals of group II of the periodic table. Illustrative of such chelates are. diheptadecylimidazoline zinc nitrate, diheptadecylimidazoline zinc chloride, diheptadecylimidazoline cadmium sulfate, diheptadecylimidazoline cadmium nitrate, diheptadecylimidazoline mercury sulfate and diheptadecylimidazoline mercury bromide.

My chelates also include those formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group II of the periodic table. Illustragroup IV of the periodic table. Illustrative of such chelates is di(heptadecylimidazoline acetic acid) lead nitrate.

Other compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group VI of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline chromium sulfate, triheptadecylimidazoline chromium nitrate and triheptadecylimidazoline chro mium chloride.

Still other compositions of my invention are the chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group VI of the periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) chromium sulfate, tri(heptadecylimidazoline acetic acid) chromium nitrate and tri(heptadecylimidazoline acetic acid) chromium The compositions of my invention also include chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group VII of the periodic table. Illustrative of such chelates are: di(heptadccylimidazoline acetic .acid) manganese nitrate, di(heptadecylimidazoline acetic acid) manganese chloride and di(heptadecylimidazoline acetic acid) manganese sulfate.

Another group of compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group VIII of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline iron sulfate, triheptadecylimidazoline iron phosphate, triheptadecylimidazoline iron nitrate, triheptadecylimidazoline cobalt sulfate and diheptadecylimidazoline nickel nitrate.

Still another group of compositions within the scope of my invention are the chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group VIII of the periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) iron sulfate, tri(heptadecylimidazoline acetic acid) iron phosphate, tri(heptadecylimidazoline acetic acid) iron nitrate, tri(heptadecylimidazoline acetic acid) cobalt sulfate and di(heptadecylimidazoline acetic acid) nickel nitrate.

Other compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri(heptadecylimidazoline) cerium acid sulfate.

Still other compositions within the scope of my invention are the chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri(heptadecylimidazoline acetic acid) cerium acid sulfate.

The compounds of the present invention can be prepared by a process which comprises bringing a 2-heptadecylimidazoline into reactive admixture with a metal salt under conditions to produce a chelate.

The metal salts which are best suited for use in this invention are water-soluble. For this reason, the reaction should be conducted in a solvent medium which comprises at least 80 percent water. Other solvents which can be used together with water are methanol, ethanol, isopropanol and pyridine. The two reactants, namely the 2-heptadecylimidazoline and the metal salt, need not be added to the solvent in any particular order. Preferably, however, in the case of 2-heptadecylimidazoline, the metal salt is dissolved in water and the 2-heptadecylimidazoline is dissolved in an alcohol, such as isopropanol, and the two solutions are combined. In the case of Z-heptadecylimidazoline acetic acid, both reactants are preferably dissolved in water.

The reaction is preferably conducted at 20 to 30 C. but can be conducted at temperatures between about C. and about 80 C.

The following examples are illustrative:

EXAMPLE I Tri(Z-heptadecylimidazoline acetic acid) chromium III nitrate (C H O N CI) was prepared as follows:

About 21 grams of chromic nitrate hydrate were dissolved in 3000 ml. of water and the solution was agitated at a slow rate. To this solution was added, dropwise over a period of minutes, 100 ml. of an isopropanol solution containing 29 grams of dissolved acetic acid salt of 2-heptadecylimidazoline. A precipitate formed and was filtered at reduced pressure in a large Buchner funnel. The precipitate was washed twice with water and dried at 50 C. and 5 mm. Hg for 24 hours. The dried precipitate had a melting point of 8284 C. The calculated percentage composition for a 100 percent pure compound 4 and the actual composition (by weight) found for the chromium III chelate are compared in Table I. In Table I, R is Z-heptadecylimidazoline acetic acid.

Table l.-Percentage composition of tri(Z-heptadecylimidazoline acetic acid) chromium III sulfate Calculated,

Percent Found. Element Composition Percent SE to Composition 1 C[(NO3)3 C 59. 0 58. 5 H 9. 9 l2. 1 O 17. 9 N 9. 4 9. 1 Cr 3. 9 3. 0

The data obtained agree satisfactorily with the theoretical structure of the chromium III chelate containing 3 moles of 2-lieptadecylimidazoline acetic acid per mole of aluminum, in accordance with the accepted coordinant number of 6 for Cr+++.

EXAMPLE II Table II.Percerztage composition of tri(Z-heptadecylimidazoline acetic acid) chromium III sulfate Calculated,

Percent Found, Element Composition Percent 3R to 1 Cr; Composition O G0. 9 58. 5 l0. 2 ll. 1 O 14. 7 14. b 0. 5 G. 0 4. 0 4. 0 3. 7 4. 5

The data obtained agree satisfactorily with the theoretical structure of the chromium IH chelate containing 3 moles of Z-heptadecylimidazoline acetic acid per mole of aluminum, in accordance with the accepted coordinant number of 6 for Cr+++.

The other chelates of this invention can be prepared in a similar manner.

As disclosed in copcnding T orgeson application, Serial No. 545,107, filed November 4, 1955, the chelates of this invention are useful as fungicides. Representative chelates contemplated herein were tested for fungicidal activity by means of the slide germination test. Essentially this test method consisted of germinating spores in continual contact, on glass slides, with given concentrations of the chemical under test. The germination was observed aftcr 24 hours and the amount of the chemical needed to inhibit germination of 50 percent (LB. 50 value) of the spores was determined. The procedure used is more fully set forth in a paper entitled The Slide-Germination Method of Evaluating Protectant Fungicides, published in Phytopathology, July 194-3, vol. XXXIII, No. 7, pp. 627-632. Two different and typical fungi were used for this test. The fungi tested were Sclerotinia fructicola (Wint.) Rehm (S.f.) and Alternaria oleracae (A.o.). The values in Table III below represent the parts by weight of the chelate under test, in a million parts by weight of liquid, to prevent the germination of 50 percent of the spores. The liquid used, which of itself did not inhibit germination of the spores, was Lins solution, which consists of grams of dextrose, 2.46 grams of MgSO -7H O and 100 ml. of distilled water. Ten milliliters of this solution were added to each 100 milliliters of spore.

Table III LDw in parts per million Compound SJ. A.o.

Dl(heptadecyllmidazoline acetic acid) sodium sulfa .31-. 62 1. 25-25 Di(heptadecylimidazoiine acetic acid) cadmium chlori e- 31-. 62 2. 5-5 Trl(heptadecylimldazoline acetic acid) aluminum sulfate 62-1. 25 2. 5-5 Tri(heptadecylimidazoilue acetic acid) chromium nitrate .3l-.62 5-10 Di(heptadecylimidazoline acetic acid) manganese chloride .62-1. 25 2.5-5 Tri(heptadecylimidazo1ine acetic acid) ferric sulfate 31-. 62 2. 5-5 Trlheptadecylimidazoline iron sulfate 62-1. 25 5-10 Diheptadecylimidazoline zincchloride .62-1. 25 5-10 The periodic table referred to in this application is the periodic table of the elements revised in accordance with the Journal of the American Chemical Society, volume 76, page 2033 (1954).

This application is a continuation-in-part of my copending application, Serial No. 545,108, filed November 4,

1955, now Patent No. 2,789,115.

I claim:

1. A chelate having the structural formula MR wherein R is a member selected from the group consisting of Z-heptadecylimidazoline and acid salts thereof, M is both the anion and cation of an inorganic salt of a metal of group VI of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

2. A chelate having the structural formula MR,

wherein R is Z-heptadecylimidazoline, M is both the anion and cation of an inorganic salt of a metal of group VI of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

3. A chelate having the structural formula MR,,, wherein R is an acid salt of 2-heptadecylimidazoline, M is both the anion and cation of an inorganic salt of a metal of group VI of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

4. A chelate having the structural formula MR,,, wherein R is Z-heptadecylimidazoline acetic acid, M is both the anion and cation of an inorganic salt of a metal of group VI of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

5. Tri(2-heptadecylimidazoline acetic acid) chromium sulfate.

6. Tri(Z-heptadecylimidazoline acetic acid) chromium nitrate.

7. Tri(2-heptadecylirnidazoline acetic acid) chromium chloride.

8. Tri(2-heptadecyiimidazoline) chromium sulfate.

9. Tri(2-heptadecylimidazoline) chromium nitrate.

10. Tri(Z-heptadecylimidazoline) chromium chloride.

References Cited in the file of this patent UNITED STATES PATENTS 2,155,877 Waldmann et a1 Apr. 25, 1939 2,540,171 Kifi Feb. 6, 1951 2,789,115 Hogsett Apr. 16, 1957 FOREIGN PATENTS 531,297 Germany Aug. 7, 1931 OTHER REFERENCES Klingenstein: Ber. Deut. Chem., vol. 28, pp. 1175-76 (1895). 

1. A CHELATE HAVING THE STRUCTURAL FORMULA MRN WHERE IN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF 2-HEPTADECYLIMUDAZOLINE AND ACID SALTS THEREOF, M IS BOTH THE ANION AND CATION OF AN INORGANIC SALT OF A METAL OF GROUP VI OF THE PERIODIC TABLE AND N IS AN INTEGER HAVING A VALUE OF ONE-HALF THE COORDINATION NUMBER OF SAID METAL. 